CN102610331B - Preparation method of electrode material of silver/graphene thin film supercapacitor - Google Patents
Preparation method of electrode material of silver/graphene thin film supercapacitor Download PDFInfo
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Abstract
The invention relates to a preparation method of an electrode material of a silver/graphene thin film supercapacitor, which comprises the steps: (1) dispersing oxidized graphite into ultrapure water at room temperature, adding silver nitrate after performing ultrasound, agitating and mixing the mixture and then adding sodium borohydride, and continuously agitating the mixture to obtain a partially reduced silver/oxidized graphite dispersion, wherein the mass ratio of sodium borohydride to oxidized graphite is 2:1-1:1; and (2) adding sodium borohydride into the partially reduced silver/oxidized graphite dispersion, raising temperature to 70-85 DEG C under nitrogen atmosphere, maintaining temperature for 1-3h, and performing centrifugal washing to obtain a silver/graphene dispersion; filtering the silver/graphene dispersion to form a film-like product; and washing the product with ultrapure water to obtain the electrode material of the silver/graphene thin film supercapacitor. The preparation method is simple and the film forming process is free from a conducting additive and a bonder, so that the preparation method is appropriate for industrialized production. The electrode material of the silver/graphene thin film supercapacitor obtained by the invention has high specific capacitance and good conducting performance, higher flexibility and wide application prospect.
Description
Technical field
The invention belongs to the preparation field of super capacitor material, particularly a kind of preparation method of silver/graphite alkene film electrode material for super capacitor.
Background technology
Graphene be can by graphite oxide reduce and a kind of new material.Since the research group of the Novoselov of University of Manchester in 2004 and Geim finds Graphene, Graphene becomes rapidly the hot issue of physics, chemistry and materialogy, has started the research boom of researcher to its character and application.Recently the researcher of Columbia Univ USA finds, Graphene is intensity maximum in known materials in the world at present, the material that thickness is the thinnest.With regard to conductivity, Graphene is zero gap semiconductor, its stable lattice structure makes carbon atom have excellent conductivity, wherein the movement velocity of electronics has reached 1/300 of the light velocity, far having exceeded the movement velocity of electronics in general conductor, is the current known outstanding material of electric conductivity.Meanwhile, Graphene has very large theoretical specific area and unique charge carrier characteristic, and this provides theoretical foundation for it becomes good electrode material for super capacitor.The people such as M.D.Stoller have reported chemical modification Graphene super capacitor material on Nano Letter 8 (2008) 3498-3452, and material prepared by this method has reached the ratio electric capacity of 135F/g in aqueous electrolyte.The people such as S.Chen have reported the graphene oxide/manganese dioxide nano-composite material for ultracapacitor on ACS Nano 4 (2010) 2822-2830, and this material has been issued to the ratio electric capacity of 197.2F/g in the current density of 200mA/g.
But, prepare now Graphene graphite oxide reducing process used conventionally, Graphene remained on surface has oxygen-containing functional group, causes some physics, chemical property loss, especially electric conductivity, this has a great impact in the application aspect ultracapacitor for Graphene.
Have not yet to see report prepared by silver/graphite alkene film electrode material for super capacitor.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of silver/graphite alkene film electrode material for super capacitor, the method technique is simple, be easy to suitability for industrialized production, prepared silver/graphite alkene film electrode material for super capacitor is higher than electric capacity, conduct electricity very well, film forming procedure is simple, without conductive agent, binding agent, there is higher flexibility, be expected to be applied to the fields such as electric automobile, communication, flexible electronic product and signal controlling.
The preparation method of a kind of silver/graphite alkene film electrode material for super capacitor of the present invention, comprising:
(1) at room temperature, graphite oxide is distributed in ultra-pure water, obtains the suspension of graphite oxide, after ultrasonic 1～2h, add silver nitrate, be uniformly mixed, add subsequently sodium borohydride, continue to obtain after stirring silver/graphite oxide dispersion liquid of partial reduction; Wherein the mass ratio of sodium borohydride and graphite oxide is 2: 1～1: 1.
(2) in silver/graphite oxide dispersion liquid of above-mentioned partial reduction, add sodium borohydride, under nitrogen atmosphere, be warming up to 70～85 ℃, insulation 1～3h, centrifuge washing obtains silver/graphite alkene dispersion liquid; Above-mentioned silver/graphite alkene dispersion liquid suction filtration is formed to membranaceous product, and ultra-pure water washing obtains silver/graphite alkene film electrode material for super capacitor.
In the suspension of the graphite oxide described in step (1), graphite oxide concentration is 0.25～0.5mg/mL.
The mass ratio of the silver nitrate described in step (1) and graphite oxide is 1: 1～5: 1.
The time being uniformly mixed described in step (1) is 20～60min.
The time that continues described in step (1) to stir is 1～3h.
The sodium borohydride adding in step (2) and the mass ratio of graphite oxide are 100: 1～50: 1.
Centrifuge washing process described in step (2) is specially: ultra-pure water centrifuge washing 5～10 times, and centrifuge speed is 6500～9000r/min, centrifugation time is 5～15min.
The number of times of the ultra-pure water washing described in step (2) is 5～10 times.
The present invention is at a certain amount of silver-colored particle of Graphene finishing, silver-colored particle forming process can be repaired the oxygen-containing functional group on Graphene surface on the one hand, the electric conductivity that silver-colored particle itself is good on the other hand can strengthen graphene conductive ability, thereby promotes the electric charge transmission in electric double layer capacitance forming process.Therefore the grapheme material of composite silver particle has more superior super capacitor performance.
The silver/graphite alkene film electrode material for super capacitor that adopts the present invention to prepare, preparation process is simple, chemical stability is good, higher than electric capacity, obviously promote with pure graphene film material phase specific capacity, there is flexible structure, in fields such as electric automobile, communication, flexible electronic product and signal controlling, have broad application prospects.
Beneficial effect
1, the method preparation technology is simple, and film forming procedure, without conductive agent, binding agent, is suitable for suitability for industrialized production;
2, the silver/graphite alkene film electrode material for super capacitor that prepared by the method is higher than electric capacity, conducts electricity very well, and has higher flexibility, is expected to be applied to the fields such as electric automobile, communication, flexible electronic product and signal controlling.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum contrast of the silver/graphite alkene prepared of embodiment 1 and pure Graphene, and illustration is the digital photograph of silver/graphite alkene film;
Fig. 2 is the silver/graphite alkene prepared of embodiment 1 and the impedance contrast collection of illustrative plates of graphene membrane electrode;
Fig. 3 is that silver/graphite alkene and graphene membrane electrode 20mV/s in 1M sodium sulphate electrolyte prepared by embodiment 1 sweeps the feature cyclic voltammetry curve figure under speed;
Fig. 4 is that silver/graphite alkene membrane electrode difference in 1M sodium sulphate electrolyte prepared by embodiment 1 is swept the feature cyclic voltammetry curve figure under speed;
Fig. 5 is the curve chart of constant current charge-discharge first of silver/graphite alkene membrane electrode different current densities in 1M sodium sulphate electrolyte of preparing of embodiment 1.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Take 0.025g graphite oxide and be distributed to ultrasonic dispersion 1h in 100mL ultra-pure water, add 0.025g silver nitrate magnetic agitation to mix 30min, add subsequently 0.04g sodium borohydride to continue to stir 2h and obtain bright brown solution.Above-mentioned solution is joined in there-necked flask; again add 2.5g sodium borohydride; under nitrogen protection atmosphere; be warming up to 80 ℃; insulation 1h; obtain black suspension, centrifugal rotational speed be the 6500r/min time be under 15min condition after ultra-pure water centrifuge washing 6 times suction filtration obtain membranaceous product, ultra-pure water washing 5 times.
Fig. 1 is the X-ray diffraction curve spectrum contrast of product and pure Graphene, in figure, there is the steamed bun peak of Graphene, several stronger diffraction maximums are mated with the PDF standard card 65-2871 of silver-colored simple substance, show to contain silver-colored particle in graphene film, do not occur that the peak of graphite oxide illustrates that it is reduced into Graphene.
Fig. 2 is the impedance contrast collection of illustrative plates of product and graphene membrane electrode, through the obvious reduction compared with 216.4 Ω of Graphene that is 50.8 Ω of the electric charge transmission resistance of the Fitting Calculation product.
Fig. 3 is that product and graphene membrane electrode 20mV/s in 1M sodium sulphate electrolyte sweep the feature cyclic voltammetry curve figure under speed, the curve that can find out product obviously broadens and is more tending towards rectangle, and the ratio electric capacity that obtains as calculated product is that the 146.3F/g of 199.4F/g and graphene film has improved 36.3%.
Fig. 4 is that difference is swept the feature cyclic voltammetry curve figure under speed in 1M sodium sulphate electrolyte.
Fig. 5 is the curve chart of constant current charge-discharge first of product different current densities in 1M sodium sulphate electrolyte, shows that product has good charge-discharge performance.
Embodiment 2
Take 0.025g graphite oxide and be distributed to ultrasonic 2h in 50mL ultra-pure water, add 0.005g silver nitrate magnetic agitation to mix 60min, add subsequently 0.025g sodium borohydride to continue to stir 1h and obtain bright brown liquid.Liquid is added in there-necked flask, again add 1.25g sodium borohydride, under nitrogen protection atmosphere, be warming up to 70 ℃, insulation 3h, obtains black liquor.Centrifugal rotational speed be the 9000r/min time be under 5min condition after ultra-pure water centrifuge washing 10 times suction filtration obtain membranaceous product, ultra-pure water washing 10 times.X-ray diffraction analysis is indicated as silver/graphite alkene compounding ingredients, and impedance analysis shows that electric charge transmission resistance is lower, and cyclic voltammetry curve analysis has higher ratio capacitive property, and constant current charge-discharge analysis has good charge-discharge performance.
Take 0.025g graphite oxide and be distributed to ultrasonic 1.5h in 80mL ultra-pure water, add 0.02g silver nitrate magnetic agitation to mix 30min, add subsequently 0.05g sodium borohydride to continue to stir 3h and obtain bright brown liquid.Liquid is added in there-necked flask, again add 1.5g sodium borohydride, under nitrogen protection atmosphere, be warming up to 85 ℃, insulation 1h, obtains black liquor.Centrifugal rotational speed be the 8000r/min time be under 10min condition after ultra-pure water centrifuge washing 5 times suction filtration obtain membranaceous product, ultra-pure water washing 7 times.X-ray diffraction analysis is indicated as silver/graphite alkene compounding ingredients, and impedance analysis shows that electric charge transmission resistance is lower, and cyclic voltammetry curve analysis has higher ratio capacitive property, and constant current charge-discharge analysis has good charge-discharge performance.
Embodiment 4
Take 0.02g graphite oxide and be distributed to ultrasonic 1.5h in 70mL ultra-pure water, add 0.01g silver nitrate magnetic agitation to mix 30min, add subsequently 0.03g sodium borohydride to continue to stir 3h and obtain bright brown liquid.Liquid is added in there-necked flask, again add 2g sodium borohydride, under nitrogen protection atmosphere, be warming up to 75 ℃, insulation 1h, obtains black liquor.Centrifugal rotational speed be the 8500r/min time be under 10min condition after ultra-pure water centrifuge washing 5 times suction filtration obtain membranaceous product, ultra-pure water washing 8 times.X-ray diffraction analysis is indicated as silver/graphite alkene compounding ingredients, and impedance analysis shows that electric charge transmission resistance is lower, and cyclic voltammetry curve analysis has higher ratio capacitive property, and constant current charge-discharge analysis has good charge-discharge performance.
Claims (6)
1. a preparation method for silver/graphite alkene film electrode material for super capacitor, comprising:
(1) at room temperature, graphite oxide is distributed in ultra-pure water, obtains the suspension of graphite oxide, after ultrasonic 1～2h, add silver nitrate, be uniformly mixed, add subsequently sodium borohydride, continue to obtain after stirring silver/graphite oxide dispersion liquid of partial reduction; Wherein the mass ratio of sodium borohydride and graphite oxide is 2:1～1:1; The mass ratio of silver nitrate and graphite oxide is 1:1～5:1;
(2) in silver/graphite oxide dispersion liquid of above-mentioned partial reduction, add sodium borohydride, under nitrogen atmosphere, be warming up to 70～85 ℃, insulation 1～3h, centrifuge washing obtains silver/graphite alkene dispersion liquid; Above-mentioned silver/graphite alkene dispersion liquid suction filtration is formed to membranaceous product, and ultra-pure water washs and get final product, and wherein the mass ratio of sodium borohydride and graphite oxide is 100:1～50:1.
2. the preparation method of a kind of silver/graphite alkene film electrode material for super capacitor according to claim 1, is characterized in that: in the suspension of the graphite oxide described in step (1), graphite oxide concentration is 0.25～0.5mg/mL.
3. the preparation method of a kind of silver/graphite alkene film electrode material for super capacitor according to claim 1, is characterized in that: the time being uniformly mixed described in step (1) is 20～60min.
4. the preparation method of a kind of silver/graphite alkene film electrode material for super capacitor according to claim 1, is characterized in that: the time of the lasting stirring described in step (1) is 1～3h.
5. the preparation method of a kind of silver/graphite alkene film electrode material for super capacitor according to claim 1, it is characterized in that: the centrifuge washing process described in step (2) is specially: ultra-pure water centrifuge washing 5～10 times, centrifuge speed is 6500～9000r/min, and centrifugation time is 5～15min.
6. the preparation method of a kind of silver/graphite alkene film electrode material for super capacitor according to claim 1, is characterized in that: the number of times of the ultra-pure water washing described in step (2) is 5～10 times.
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| CN103779575A (en) * | 2012-10-23 | 2014-05-07 | 海洋王照明科技股份有限公司 | Graphene/metal composite current collector and preparation method thereof |
| CN103334096B (en) * | 2013-07-02 | 2015-12-23 | 江苏大学 | A kind of method preparing nano-silver-graphenecomposite composite film |
| CN103413696B (en) * | 2013-08-29 | 2015-12-23 | 电子科技大学 | A kind of method manufacturing the flexible electrode that nano silver colloid is modified |
| CN103545053B (en) | 2013-10-25 | 2016-03-09 | 深圳市华星光电技术有限公司 | The preparation method of transparent conductive film and there is the preparation method of CF substrate of this conductive film |
| CN104384524B (en) * | 2014-11-19 | 2017-07-18 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of flake graphite alkene single multi- supported precious metal nano-particle |
| TWI642735B (en) * | 2015-01-16 | 2018-12-01 | 欣興電子股份有限公司 | Conductive ink, circuit board and method for manufacturing the same |
| CN106898435B (en) * | 2017-03-10 | 2019-04-09 | 东华大学 | A kind of preparation method of high-bulk-density flexible electrode material |
| CN107233803B (en) * | 2017-06-02 | 2020-05-19 | 青岛大学 | Graphene/silver particle composite filter film and preparation and application thereof |
| CN113658744B (en) * | 2021-07-19 | 2022-06-07 | 重庆文理学院 | Flexible conductive composite cotton thread and preparation method thereof |
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